Extrudable pressure sensitive adhesive composition and methods for preparing the same

ABSTRACT

A phase-separated polymeric composition comprising a first phase including polyurethane domains; and a second phase including a butyl rubber matrix.

This application is a continuation of U.S. Ser. No. 13/643,669, filed onMar. 7, 2013, which is a national-stage application of InternationalApplication Serial No. PCT/US11/34270, filed on Apr. 28, 2011, whichclaims the benefit of U.S. Provisional Application Ser. No. 61/329,207,filed on Apr. 29, 2010, all of which are incorporated herein byreference.

FIELD OF THE INVENTION

Embodiments of the present invention are directed toward extrudablepressure sensitive adhesive compositions and methods for making thesame; the compositions are particularly useful as a seaming tape forpolymeric roofing membranes.

BACKGROUND OF THE INVENTION

Flat or low-sloped roofs are often covered with polymeric membranes,which protect the roof from environmental impact such as snow and rain.

These polymeric membranes are typically manufactured and shipped inwidths that are narrower than the roof surface to which they areinstalled. Accordingly, multiple membranes are often installed, andadjacent membranes are seamed together.

Pressure sensitive seam tapes are often employed for this purpose.Specifically, a pressure sensitive seam tape is applied to one surfaceof a membrane along a longitudinal edge and an adjacent membrane ismated along its longitudinal edge to the top surface of the pressuresensitive seam tape to thereby form a seam.

Technologically useful pressure-sensitive seam tapes employed in theindustry include cured or partially cured rubber. For example, U.S. Pat.No. 4,855,172 teaches an adhesive tape comprising cured butyl rubber.The rubber can be cross-linked with a bromomethylated phenolic resin andzinc oxide. The composition is typically manufactured by extruding alayer of green or uncured rubber to a coated release paper, rolling theextrudate and release paper, and then subjecting it to curing conditionsfor a specified period of time (e.g., one day at 70° C.). Similarly,U.S. Pat. No. 5,242,727 teaches a pressure-sensitive adhesive tapecomposition including a blend of an ethylene-propylene-diene terpolymer,a halogenated butyl rubber, polyisobutylene, a phenolic resin, zincoxide, and a sulfur-based cure system. After the composition is extrudedonto a release liner, it is heated to a temperature of about 100° C. fora period of two-six hours to achieve the desired cross-linking of therubber.

While these pressure-sensitive adhesive tapes have proven to betechnologically useful, they suffer from several drawbacks. First, theyrequire significant cure time, which reduces manufacturing efficienciesand increases costs. Also, due to the level of curing, the compositionsbehave as thermoset materials and are therefore not reprocessable.

There is therefore a desire for pressure-sensitive adhesive tapecompositions that are more easily manufactured, are reprocessable, anddemonstrate the performance characteristics that have come to beexpected from cured butyl rubber systems.

SUMMARY OF THE INVENTION

One or more embodiments of the present invention provide aphase-separated polymeric composition comprising a first phase includingpolyurethane domains; and a second phase including a butyl rubbermatrix.

Still other embodiments of the present invention provide a method forproducing a polymeric composition, the method comprising providing ahalogenated butyl rubber including one or more halogen atoms and one ormore double bonds deriving from isoprene; partially cross-linking thebutyl rubber by displacement of two or more of the halogen atoms by ametal oxide; chemically binding a phenolic resin across one or more ofthe double bonds to provide the butyl rubber with a hydroxylfunctionality; chemically binding an isocyanate to at least one hydroxylfunctionality of the butyl rubber to form a butyl rubber/urethanemacromolecule; and forming a polyurethane in the presence of the butylrubber/urethane macromolecule.

Still other embodiments of the present invention provide a method forproducing a polymeric composition, the method comprising charginghalogenated butyl rubber to a reaction extruder; charging a firstphenolic resin to the reaction extruder, where the first phenolic resinincludes functionality for reacting with double bonds located on thebutyl rubber; charging a second phenolic resin that is substantiallydevoid of functionality for reacting with double bonds located on thebutyl rubber; charging a metal oxide to the reaction extruder; charginga catalyst to promote a reaction between the butyl rubber and the firstphenolic resin to the reaction extruder; mixing said halogenated butylrubber, said first phenolic resin, said metal oxide, and said catalystto promote the reaction between the butyl rubber and the first phenolicresin to thereby partially crosslinking the rubber and functionalizingthe rubber with the first phenolic resin; charging a isocyanate to thereaction extruder; and mixing said partially crosslinked rubber, saidphenolic resin, and said catalyst to thereby form a polyurethanedispersed within butyl rubber.

Still other embodiments of the present invention provide a method forproducing a polymer composition, the method comprising providing amasterbatch composition that is prepared by combining a halogenatedbutyl rubber with a phenolic resin; introducing the masterbatchcomposition to a reactor; introducing to the reactor an isocyanate and acatalyst for forming a polyurethane to form a blend; and subjecting theblend to conditions sufficient to form a polyurethane.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart showing a process for preparing compositions ofone or more embodiments of the present invention.

FIG. 2 is a schematic showing a process for making compositions of oneor more embodiments of the invention within a continuous extruder.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

Embodiments of the present invention are directed towardpressure-sensitive adhesive compositions that include polyurethanedomains dispersed within a butyl rubber matrix. In one or moreembodiments, the polyurethane may be formed by reacting an isocyanatewith a phenolic resin. And, the butyl rubber may be partiallycrosslinked and may be reacted or functionalized with a phenolic resin.

In one or more embodiments, the composition may be produced by providinga partially-crosslinked butyl rubber and forming a polyurethane in thepresence of the partially-crosslinked butyl rubber. In one or moreembodiments, the partially-crosslinked butyl rubber may be produced bycombining a halogenated butyl rubber with a phenolic resin (e.g. a firstphenolic resin) and optionally a metal catalyst. The polyurethane isformed in the presence of the partially-crosslinked butyl rubber byreacting an isocyanate with the first phenolic resin and/or a secondphenolic resin in the presence of a catalyst for the polyurethane.Processing oil may be added to the composition, along with otherconventional additives, at various stages of the process. In particularembodiments, the compositions can be manufactured continuously within areactive extruder.

Ingredients

In preparing the compositions of the present invention, one or more ofthe following ingredients may be employed.

In one or more embodiments, butyl rubber includes copolymers andterpolymers of isobutylene and at least one other comonomer. Usefulcomonomers include isoprene, divinyl aromatic monomers, alkylsubstituted vinyl aromatic monomers, and mixtures thereof. Exemplarydivinyl aromatic monomers include vinyl styrene. Exemplary alkylsubstituted vinyl aromatic monomers include a-methyl styrene andparamethyl styrene. These copolymers and terpolymers may also behalogenated such as in the case of chlorinated and brominated butylrubber. In one or more embodiments, these halogenated polymers mayderive from monomer such as parabromomethylstyrene.

In one embodiment, where butyl rubber includes an isobutylene-isoprenecopolymer, the copolymer may include from about 0.5 to about 30, or inother embodiments from about 0.8 to about 5, percent by weight isoprenebased on the entire weight of the copolymer with the remainder beingisobutylene.

In the case of halogenated butyl rubbers, the butyl rubber may includefrom about 0.1 to about 10, or in other embodiments from about 0.3 toabout 7, or in other embodiments from about 0.5 to about 3 percent byweight halogen based upon the entire weight of the copolymer orterpolymer.

In one or more embodiments, the glass transition temperature (Tg) ofuseful butyl rubber can be less than about −55° C., or in otherembodiments less than about −58° C., or less than about −60° C., or inother embodiments less than about −63° C.

In one or more embodiments, the Mooney viscosity (ML₁₊₈@125° C.) ofuseful butyl rubber can be from about 25 to about 75, or in otherembodiments from about 30 to about 60, or in other embodiments fromabout 40 to about 55.

Useful butyl rubber includes those prepared by polymerization at lowtemperature in the presence of a Friedel-Crafts catalyst as disclosedwithin U.S. Pat. Nos. 2,356,128 and 2,944,576, which are incorporatedherein by reference. Other methods may also be employed.

Butyl rubber can be obtained from a number of commercial sources asdisclosed in the Rubber World Blue Book. For example, halogenatedcopolymers of isobutylene and isoprene are available under the tradenameExxon Butyl™ (ExxonMobil Chemical Co.), halogenated and un-halogenatedcopolymers of isobutylene and paramethyl styrene are available under thetradename EXXPRO™ (ExxonMobil Chemical Co.), star branched butyl rubbersare available under the tradename STAR BRANCHED BUTYL™ (ExxonMobilChemical Co.), and brominated isobulylene-isoprene copolymer with highMooney viscosity is available under the tradename Lanxess Bromobutyl X2(Lanxess, Inc.).

The first phenolic resin includes a functionalized phenolic resin, whichrefers to a phenolic resin including one or more functionality forreacting with double bonds located within butyl rubber. In general, theterm phenolic resin refers to the reaction products of a phenol orsubstituted phenol with an aldehyde such as formaldehyde. The firstphenolic resin may also be referred to as a reactive or functionalizedphenolic resin.

In one or more embodiments, the functionality for reacting with doublebonds within butyl rubber include, but are not limited to, halogenatoms, halogenated hydrocarbyl groups, and hydroxyl orcarboxyl-containing hydrocarbyl group. Where the functionality is ahydroxyl group, those skilled in the art will appreciate that thishydroxyl functionality is distinct from the hydroxyl functionalitydirectly attached to a phenol ring of the resin.

In one or more embodiments, the reactive phenolic resins may includethose defined according to the general formula

where each R¹ is independently a divalent organic group, each R² isindependently a monovalent organic group, each X is independently afunctional group or monovalent organic group containing a functionalgroup, and m is an integer from 0 to 20.

In one or more embodiments, mono-valent organic groups may includehydrocarbyl groups or substituted hydrocarbyl groups such as, but notlimited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, allyl,aralkyl, alkaryl, or alkynyl groups. Substituted hydrocarbyl groupsinclude hydrocarbyl groups in which one or more hydrogen atoms have beenreplaced by a substituent such as an alkyl group. In one or moreembodiments, these groups may include one, or the appropriate minimumnumber of carbon atoms to form the group, to 20 carbon atoms. Thesegroups may contain heteroatoms such as, but not limited to, nitrogen,boron, oxygen, silicon, sulfur, tin, and phosphorus atoms.

In one or more embodiments, divalent organic groups may includehydrocarbylene groups or substituted hydrocarbylene groups such as, butnot limited to, alkylene, cycloalkylene, alkenylene, cycloalkenylene,alkynylene, cycloalkynylene, or arylene groups. Substitutedhydrocarbylene groups include hydrocarbylene groups in which one or morehydrogen atoms have been replaced by a substituent such as an alkylgroup. In one or more embodiments, these groups may include one, or theappropriate minimum number of carbon atoms to form the group, to 20carbon atoms. These groups may also contain one or more heteroatoms suchas, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, tin,and phosphorus atoms.

In one or more embodiments, the divalent organic groups may includeether groups. For example, R¹ may include a group defined by the formula

—CH²—O—CH²—

In particular embodiments, each R¹ is a divalent ether group having theformula —CH²—O—CH²—, m is an integer from 0 to 10, each R² is amonovalent organic group having 12 or less carbon atoms, and X is abromomethyl group or methylol group.

In one or more embodiments, at least 50%, in other embodiments at least95%, and in other embodiments at least 99% of the monovalent organicgroups R² are located in the para position. In these or otherembodiments, at least 50%, in other embodiments at least 95%, and inother embodiments at least 99% of the monovalent organic groups R² arebranched alkyl group; for example, branched monovalent organic group,which also may be referred to as sterically hindered monovalent organicgroups, may include tert-butyl groups, neo-pentyl groups, and tert-octylgroups.

In one or more embodiments, the functional group X may be a halogen atomselected from the group consisting of bromine, chlorine, and iodine. Inother embodiments, the functional group X may be a halogen-containingmonovalent organic group such as, but not limited to, a chloromethylgroup or bromomethyl group. In other embodiments, the functional group Xmay be an alkylol group such as a methylol group, a propylol group, abutylol group, or a pentylol group.

In one or more embodiments, the first phenolic resin is a resole resin,which can be made by the condensation of alkyl substituted phenols orunsubstituted phenols with aldehydes, such as formaldehyde, in analkaline medium or by condensation of bi-functional phenoldialcohols.

Functionalized phenolic resins may be obtained under the tradenamesSP-1044, SP-1045, and SP-1055 (Schenectady International; Schenectady,N.Y.). SP-1045 is believed to be an octylphenol-formaldehyde resin thatcontains terminal methylol groups. SP-1055 is believed to be anoctylphenol-formaldehyde resin that contains terminal bromomethylgroups.

The second phenolic resin is devoid or substantially devoid of terminalfunctional groups. In one or more embodiments, the second phenolic resinis unreactive or substantially unreactive with butyl rubber, andtherefore the second phenolic resin may also be referred to asunfunctionalized or unreactive phenolic resin.

In one or more embodiments, the unreactive phenolic resin may includethose defined by the formula

where each R³ is independently a divalent organic group, each R² isindependently a monovalent organic group, and m is an integer from 0 to20.

In one or more embodiments, each R³ is devoid of heteroatoms. In theseor other embodiments, each R² is devoid of heteroatoms. In these orother embodiments, each R² is a sterically hindered or highly branchedalkyl group. In one or more embodiments, each phenol substituent withinthe resin may include further substitution (i.e., one or more hydrogenatoms attached to the phenol ring may be replaced with an aklyl group);the substituents that form the substituted phenol are devoid ofheteroatoms.

In one or more embodiments, the second phenolic resin is a resole resin,which can be made by the condensation of alkyl, substituted phenols, orunsubstituted phenols with aldehydes such as formaldehyde in an alkalinemedium or by condensation of bi-functional phenoldialcohols. In one ormore embodiments, this condensation reaction occurs in the excess ormolar equivalent of formaldehyde. In other embodiments, the secondphenolic resin may be formed by an acid-catalyzed reaction.

Unfunctionalized phenolic resins may be obtained under the tradenameSP-1068 (Schenectady International; Schenectady, N.Y.). SP-1068 isbelieved to be an octylphenol-formaldehyde resin that is devoid orsubstantially devoid of terminal functional groups such as halogen atomsor methylol groups.

In one or more embodiments, useful isocyanates include aromaticpolyisocyanates such as diphenyl methane diisocyanate in the form of its2,4′-, 2,2′-, and 4,4′-isomers and mixtures thereof, the mixtures ofdiphenyl methane diisocyanates (MDI) and oligomers thereof known in theart as “crude” or polymeric MDI having an isocyanate functionality ofgreater than 2, toluene diisocyanate in the form of its 2,4′ and2,6′-isomers and mixtures thereof, 1,5-naphthalene diisocyanate, and1,4′ diisocyanatobenzene. Exemplary isocyanate components includepolymeric Rubinate 1850 (Huntsmen Polyurethanes), Rubinate 9433(Huntsmen Polyurethanes), polymeric Lupranate M70R (BASF), and polymericMondur 489N (Bayer).

In one or more embodiments, the metal catalysts may be metal oxides thatmay be employed to crosslink the halogenated butyl rubber include alkalimetal oxides, alkali earth metal oxides, and transition metal oxides. Inparticular embodiments, the metal oxide is magnesium oxide, and in otherembodiments the metal oxide is calcium oxide. While it is believed thatthe metal oxide reacts with the halogen atom of the halogenated butylrubber to form crosslinks, the metal oxide may also serve to catalyze areaction between the halogenated butyl rubber and the reacted phenolicresin. In other embodiments, the metal catalyst may be an organometalsuch as magnesium resinate.

In one or more embodiments, the catalyst for polyurethane, which mayalso be referred to as polyurethane catalyst, which is believed topromote a reaction between the unfunctionalized phenolic resin and theisocyanate, is an amine compound. Useful amine compounds include thosethat promote a reaction between a polyol and an isocyanate (which isknown as a gel reaction), those that promote a reaction between waterand icocyanate (which is known as a blow reaction), and those catalyststhat promote isocyanate trimerization. Exemplary amine catalysts includetriethylenediamine (TEDA), dimethylcyclohexylamine (DMCHA),dimethylethanolamine (DMEA), tetramethylbutanediamine (TMBDA),pentamethyldipropylenetriamine,N-(3-dimethylaminopropyl)-N,N-diisopropanolamine,1,3,5-(tris(3-dimethylamino)propyl)-hexahydro-s-triazine,bis-(2-dimethylaminoethyl)ether, N-ethylmorpholine, triethylamine (TEA),1,8-diazabicyclo[5.4.0]undecene-7(DBU), pentamethyldiethylenetriamine(PMDETA), benzyldimethylamine (BDMA), pentamethyldiethylene triamine(PMDETA), 2,4,6-tris[(dimethylamino)methyl]phenol, tributyl amine,N-methyl morpholine, and N-ethyl morpholine.

In one or more embodiments, the compositions of the present inventionmay include oil, which may also be referred to as processing oil orextender oil. These extenders may include high-boiling hydrocarbons.Examples of these oils include paraffinic oils, aromatic oils,naphthenic oils, vegetable oils, and low PCA oils including MES, TDAE,and SRAE, and heavy naphthenic oils, and various synthetic oils such as,but not limited, polybutene oils. In one or more embodiments, the oilemployed is selected based upon its compatibility with the rubber, aswell as its ability to provide advantageous properties to the finalcomposition (e.g., green strength or tack).

In particular embodiments, a polybutene oil is employed. Usefulpolybutene oils include high-viscosity oils that may be characterized bya viscosity at 100° C. of at least 80 cst, in other embodiments at least100 cst, or in other embodiments at least 120 cst up to, for example,about 700 or 800 cst. In these or other embodiments, the high viscositypolybutene oils may be characterized by a molecular weight of at least1000 g/mole, in other embodiments at least 1200 g/mole, or in otherembodiments at least 1300 g/mole up to, for example, 1400 or 1500g/mole. An exemplary high-viscosity polybutene oil is available underthe tradename Indapol H300 (Ineos) or PB32 (Soltex).

In these or other embodiments, oils or extenders may be used as carriersfor one or more of the various ingredients employed in preparing thecompositions. When used as a carrier, the oils may, especially where itmay be disadvantageous to heat the oil (e.g., when used as a carrier fora catalyst), include low viscosity or low molecular weight oils. Inother words, where a low molecular weight or low viscosity oil isemployed, the oil, along with the constituent that it carries, can beinjected into the composition without heating. Exemplary low-viscosityoils may be characterized by a viscosity at 100° C. of less than 80 cst,in other embodiments less than 70 cst, or in other embodiments less than60 cst. In these or other embodiments, these low-viscosity oils may becharacterized by a molecular weight of less than 100 g/mole, or in otherembodiments less than 700 g/mole. An exemplary low-viscosity oil is apolybutene oil available under the tradename Indapol H25 (Ineos).

Other oils that may be employed include carriers for the isocyanatecomponent. That is, because the solubility of the isocyanate may bedistinct from other components of the composition, particular oils orcarriers may need to be selected. In particular embodiments, aromaticoils are used as carriers for the isocyanate component. An exemplaryaromatic oil includes that of available under the tradename HB40(Solutia). Other useful oils include Ruetasolv DI (Rutgers), which is adiisopropyl naphthalene, which is advantageously both a low-viscosityoil and an oil that is compatible with the isocyanate.

In one or more embodiments, the compositions of the present inventionmay include fillers or pigments such as an organic filler and/orinorganic filler. Useful organic fillers include carbon blacks, coalfiller, and ground recycled rubber. Useful inorganic fillers includeclays, talc, mica, titanium dioxide, calcium carbonate, and silica.

In one or more embodiments, useful carbon blacks include those generallycharacterized by average industry-wide target values established in ASTMD-1765. Exemplary carbon blacks include GPF (General-Purpose Furnace),FEF (Fast Extrusion Furnace), and SRF (Semi-Reinforcing Furnace). Oneparticular example of a carbon black is N650 GPF Black, which is apetroleum-derived reinforcing carbon black having an average particlesize of about 60 nm and a specific gravity of about 1.8 g/cc. Anotherexample is N330, which is a high abrasion furnace black having anaverage particle size about 30 nm, a maximum ash content of about 0.75%,and a specific gravity of about 1.8 g/cc.

Useful clays include hydrated aluminum silicates. In one or moreembodiments, useful clays can be represented by the formulaAl₂O₃SiO₂.XH₂O. Exemplary forms of clay include kaolinite,montmorillonite, atapulgite, illite, bentonite, halloysite, and mixturesthereof. In one embodiment, the clay is represented by the formulaAl₂O₃SiO₂.3H₂O. In another embodiment, the clay is represented by theformula Al₂O₃SiO₂.2H₂O. In a preferred embodiment, the clay has a pH ofabout 7.0.

Useful talc include hydrated magnesium silicate. In one or moreembodiments, talc can be represented by the formulae Mg₃Si₄O₁₀(OH)₂ or3MgO.4SiO₂.H₂O. Exemplary forms of talc include talcum, soapstone,steatite, cerolite, magnesium talc, steatite-massive, and mixturesthereof. Talc filler may contain various other minerals such asdolomite, chlorite, quartz, and the like. Talc used as filler may alsoexhibit characteristics such as hydrophobicity, organophilicity,non-polarity, and chemically inertness. In one embodiment, the talc hasa specific gravity of from about 2.6 to about 2.8, a pH of from about7.0 to 8.7, a refractive index of about 1.57 at 23° C., and a moisturecontent of less than about 0.5 weight percent. A representative talc isTalc 9107, which is available from Polar Minerals (Mt. Vernon, Ind.),which is non-abrasive, chemically inert, has a specific gravity of about2.8, a pH of about 8.7, a refractive index of about 1.57 at 23° C., anda moisture content of less than about 0.3 weight percent.

In addition to the foregoing constituents, the membranes of thisinvention may also optionally include homogenizing agents, processingaids such as waxes, flame retardants, zinc oxide, stearic acid,antioxidants, antiozonants, processing additives, fillers, such asreinforcing and non-reinforcing carbon blacks, and mixtures thereof.Certain embodiments may be substantially devoid of any of theseconstituents.

Preparation of Composition

In one or more embodiments, the adhesive compositions may prepared byproviding a partially-crosslinked butyl rubber and forming apolyurethane in the presence of the partially-crosslinked butyl rubber.In one embodiment, the adhesive compositions are prepared in acontinuous process that may also be referred to as an in-line process.In other embodiments, the adhesive compositions are prepared by atwo-step process that may also be referred to as a masterbatch process.In either embodiment, the partially-crosslinked butyl rubber may beformed by combining a halogenated butyl rubber with a phenolic resin.The polyurethane is formed in the presence of the partially-crosslinkedbutyl rubber by reacting an isocyanate with a phenolic resin in thepresence of a polyurethane catalyst. In one or more embodiments, thepolyurethane in formed under conditions of mixing including, but notlimited to, high shear mixing.

Where an in-line process is employed, the partially-crosslinked butylrubber is formed by combining a halogenated butyl rubber with a firstphenolic resin. The combination of the halogenated butyl rubber and thefirst phenolic resin takes place within a reactor (e.g., extrusionreactor) wherein the polyurethane is formed. Within this process, thehalogenated butyl rubber and the first phenolic resin (which is areactive resin) are combined in the presence of a metal catalyst (e.g.,metal oxide) that is employed for assisting in the crosslinking of therubber.

In one or more embodiments, the butyl rubber may be at least partiallycrosslinked through interaction or reaction with the first phenolicresin (i.e., functionalized phenolic resin), the metal catalyst (e.g.,metal oxide), or both. Without wishing to be bound by any particulartheory, it is believed that crosslinks are formed between double bondslocated on the butyl rubber through a reaction with the first phenolicresin and between halogen sites located on the butyl rubber through areaction or interaction with the metal catalyst (e.g., metal oxide). Inone or more embodiments, the reaction between the first phenolic resinand the butyl rubber takes place in the presence of the metal catalyst(e.g., metal oxide), which may also serve to catalyze the reactionbetween the first phenolic resin and the double bonds of the butylrubber.

In one or more embodiments, the polyurethane is formed by reacting anisocyanate with hydroxyl groups of a second phenolic resin andoptionally hydroxyl groups of the first phenolic resin. It is believedthat the isocyanate may react with terminal hydroxyl groups or hydroxylgroups attached directly to the phenyl ring of the phenolic resins.Without wishing to be bound by any particular theory, it is believedthat the first phenolic resin may react with both the butyl rubber andthe isocyanate (i.e., take part in the polyurethane reaction) andthereby chemically link polyurethane to butyl rubber.

In one or more embodiments, a reaction scheme for preparing the adhesivecomposition within an in-line process can be described with reference toFIG. 1. The process 10 includes introducing halogenated butyl rubber 12with the first (functionalized) phenolic resin 14 to form acrosslinkable blend 16. The crosslinkable blend 16 may be prepared inthe presence of a metal catalyst 20. An oil 18 (e.g. high-viscositypolybutene oil) may be added to blend 16 after its formation.

Crosslinkable blend 16 is then crosslinked in the presence of thefunctionalized phenolic resin 14 and/or metal oxide 20, as well as anyof the other ingredients that may optionally be present during thecrosslinking step, to form partially-crosslinked rubber 26. Inparticular embodiments, polyurethane catalyst 24 is added to partiallycrosslinked rubber 26 after its formation. Polyurethane catalyst 24 maybe carried by carrier oil 25 (e.g., low viscosity oil). Oil 18 may alsobe introduced after formation of partially crosslinked rubber 26.

In one or more embodiments, isocyanate 28 is introduced to thepartially-crosslinked rubber 26 following introduction and mixing ofpolyurethane catalyst 24. In particular embodiments, isocyanate 28 ispre-blended in an oil 27 (e.g. aromatic oil) prior to introduction withpartially crosslinked rubber 26. Isocyanate 28 reacts withfunctionalized phenolic resin 14 and/or second phenolic resin 22 in whatis believed to be a polyurethane reaction in the presence of partiallycrosslinked butyl rubber 26 to form extrudable adhesive 30. In one ormore embodiments, second phenolic resin 22 can be introduced tocrosslinkable blend 16 before or after formation of the partiallycrosslinked rubber 26

In one or more embodiments, the step of partially crosslinking the butylrubber takes place at a temperature of from about 82.2° C. to about 132°C., in other embodiments from about 93.3° C. to about 124° C., and inother embodiments from about 98.9° C. to about 113° C.

In one or more embodiments, after forming the partially-crosslinkedbutyl rubber 26, the temperature of the composition may be increased (orallowed to increase). For example, after formation ofpartially-crosslinked butyl rubber 26 and before the introduction ofisocyanate 28, the temperature of the composition may be increased fromabout −12° C. to about 0° C., or in other embodiments from about −9.4°C. to about −3.9° C., over the temperature of the composition duringpartial crosslinking of the rubber.

In these or other embodiments, after the step of reacting isocyanate 28to form a polyurethane in the presence of partially crosslinked butylrubber 26 takes place, the temperature of the composition may be reducedprior to exiting the extruder. For example, the temperature may becooled to about 82.2° C. to about 104° C., and in other embodiments fromabout 87.8° C. to about 98.9° C.

In other embodiments, the halogenated butyl rubber and anunfunctionalized phenolic resin (e.g. the second phenolic resin) may becombined in a separate reactor and thereby form a masterbatch that issubsequently delivered to a reactor where the polyurethane is formed. Inother words, the masterbatch can be prepared by reacting the halogenatedbutyl rubber with an un-functionalized phenolic resin (i.e., the secondphenolic resin described above). It has advantageously been discoveredthat when the halogenated butyl rubber and second phenolic resin (i.e.,un-functionalized phenolic resin) are combined and given adequate timeto react, a partially-crosslinked butyl rubber can be formed in theabsence of a metal oxide and/or without the use of a functionalizedphenolic resin. The masterbatch can be prepared in any conventionalbatch-mixing equipment such as a sigma-blade mixer, a Banbury mixer or aBrabender mixer.

The reaction between the un-functionalized phenolic resin (e.g. secondphenolic resin) and the halogenated butyl rubber may take place at atemperature of from about 76.7° C. to about 116° C. or in otherembodiments from about 82.2° C. to about 104° C. In particularembodiments, the reaction time for forming the masterbatch may be fromabout 1 to about 10 minutes or in other embodiments from about 3 toabout 6 minutes under mixing conditions.

Once the masterbatch of the partially-crosslinked butyl rubber isprepared, the partially-crosslinked butyl rubber can be transferred to asecond reactor wherein the polyurethane is formed in the presence of thepartially-crosslinked butyl rubber. For example, thepartially-crosslinked butyl rubber can be transferred to a reactionextruder wherein the polyurethane is formed. Together with thepartially-crosslinked butyl rubber, additional un-functionalizedphenolic resin (i.e., second phenolic resin) can be charged to thereactor. Then, in a manner similar to the in-line procedure,polyurethane catalyst and isocyanate can be charged to the reactor toform the polyurethane in the presence of the partially-crosslinked butylrubber.

A variety of rubber and/or plastic processing equipment can be employedin the in-line process, as well as the masterbatch process. For example,the compositions can be prepared in continuous-mixing apparatus such astwin-screw or planetary extruders. In a particular embodiment, thecomposition is prepared within a continuous extruder. The extruder canhave dimensions, in terms of length to diameter (L/D), of at least 40/1,in other embodiments at least 45/1, and in other embodiments equal to orat least 50/1. As in generally known in the art, extruders of thisnature (which may also be referred to as reaction extruders), mayinclude a plurality of barrels, and within each barrel two or morescrews may be positioned. These screws can be equipped with a variety ofscrew elements, which elements can accomplish a variety of mixingparameters including, without limitation, conveying, high intensitymixing, kneading, and backmixing. Each barrel can be heated or cooled asdesired, ingredients can be added at one or more barrels, and gases canbe removed at one or more barrels.

FIG. 2 shows exemplary extruder 40. In one or more embodiments, thesolid ingredients 52, such as halogenated butyl rubber 12,functionalized phenolic resin 14, metal oxide 20, and unfunctionalizedphenolic resin 22, are introduced in the feed throat 42 of extruder 40.The pelletized ingredients may be added by way of a pellet feeder andthe powdered ingredients may be added by way of a powder feeder. Theseingredients are mixed and a temperature of about 82.2° C. to about 93.3°C. is maintained for about the first 2/5 (i.e. about 24 L/D) of theextruder to at least partially crosslink the rubber in the case of thein-line process. The polyurethane catalyst 24 (e.g. dispersed within acarrier oil) is then introduced at a downstream injection point 44,which may be at a barrel located at about 24 L/D, and mixing iscontinued for about another 12 L/D to disperse the polyurethane catalystin the partially crosslinked rubber. Together with the introduction ofpolyurethane catalyst 24 or shortly thereafter, the temperature of thecomposition may be increased (e.g. 93.3° C.-121° C.). The isocyante 28is then introduced (e.g. dispersed within a carrier oil) at a subsequentinjection point 46, which may be at a barrel located at about 36 L/D,and mixing is continued for about another 12 L/D to form extrudableadhesive 30. Following introduction of the isocyanate and initialformation of the polyisocyanate, the temperature of the composition maybe reduced (e.g., 82.2-104° C.) in order to facilitate furtherprocessing of the composition after leaving the extruder (e.g., placingthe composition on a release paper or film). High viscosity oil 18 maybe added at various locations in the process. For example, oil may beinjected at barrels located about 3/10 L/D and 7/10 L/D as shown in FIG.2.

In one or more embodiments, extrudable adhesive 30 may be extrudedthrough a die 48. The die may positioned directly to or adjacent toextruder 40, or additional extruders (not shown) may be employed. Thedie may be used to form a generally planar extrudate that may bedeposited onto a release paper of film 49. The resulting laminate (i.e.adhesive deposited onto release paper or film) may then be wound forsubsequent storage, transport, and use.

Ingredient Amounts

In one or more embodiments, the compositions of the present inventionmay be prepared by providing to the reactor at least 25 percent byweight, in other embodiments at least 30 percent by weight, and in otherembodiments at least 35 percent by weight halogenated butyl rubber basedon the total weight of the composition. In these or other embodiments,the compositions of the present invention can be prepared by providingless than 60 percent by weight, in other embodiments less than 55percent by weight, and in other embodiments less than 50 percent byweight halogenated butyl rubber based on the total weight of thecomposition. In one or more embodiments, the amount of butyl rubber fedto the reactor may be from about 25 to about 60, in other embodimentsfrom about 30 to about 50, and in other embodiments from about 35 toabout 55 percent by weight, based upon the total weight of thecomposition.

In one or more embodiments, the compositions of the present inventioncan be prepared, particularly in those embodiments employing an in-linemanufacturing technique, by providing to the reactor at least 1 percentby weight, in other embodiments at least 2 percent by weight, and inother embodiments at least 4 percent by weight of the first phenolicresin (reactive resin) based on the total weight of the composition. Inthese or other embodiments, the compositions of the present inventioncan be prepared by providing less than 30 percent by weight, in otherembodiments less than 20 percent by weight, and in other embodimentsless than 15 percent by weight first phenolic resin (reactive resin)based on the total weight of the composition. In one or moreembodiments, the amount of first phenolic resin fed to the reactor maybe from about 1 to about 30, in other embodiments from about 2 to about20, and in other embodiments from about 4 to about 15 percent by weight,based upon the total weight of the composition.

In one or more embodiments, the compositions of the present inventioncan be prepared, particularly in those embodiments employing an in-linemanufacturing technique, by providing to the reactor at least 5 percentby weight, in other embodiments at least 6 percent by weight, and inother embodiments at least 7 percent by weight second phenolic resin(non-reactive resin) based on the total weight of the composition. Inthese or other embodiments, the compositions of the present inventionmay be prepared by providing to the reactor less than 15 percent byweight, in other embodiments less than 12 percent by weight, and inother embodiments less than 10 percent by weight second phenolic resin(non-reactive resin) based on the total weight of the composition. Inone or more embodiments, the amount of second phenolic resin fed to thereactor may be from about 5 to about 15, in other embodiments from about6 to about 12, and in other embodiments from about 7 to about 10 percentby weight, based upon the total weight of the composition.

Where a master-batch manufacturing technique is employed, thecompositions may be prepared by providing to a first reactor at least 10percent by weight, in other embodiments at least 12 percent by weight,and in other embodiments at least 15 percent by weight second phenolicresin (non-reactive resin) based on the total weight of the masterbatch.In these or other embodiments, the masterbatch may be prepared byproviding to the reactor less than 22 percent by weight, in otherembodiments less than 20 percent by weight, and in other embodimentsless than 18 percent by weight second phenolic resin (non-reactiveresin) based on the total weight of the masterbatch. Upon adding themasterbatch to the reactor where the polyurethane is formed, additionalamounts of the second phenolic resin may be added; for example,additional phenolic resin may be added in an amount up to 10 weightpercent, in other embodiments up to 7 weight percent, and in otherembodiments up to 4 weight percent based upon the entire weight of thecomposition. In one or more embodiments, the amount of second phenolicresin used to prepare the master-batch may be from about 10 to about 22,in other embodiments from about 12 to about 20, and in other embodimentsfrom about 15 to about 18 percent by weight, based upon the total weightof the masterbatch.

In one or more embodiments, the compositions of the present inventioninclude at least 1 in other embodiments at least 2, and in otherembodiments at least 4 percent by weight isocyanate based on the totalweight of the composition. In these or other embodiments, thecompositions of the present invention include less than 10 in otherembodiments less than 8, and in other embodiments less than 6 percent byweight isocyanate based on the total weight of the composition. In oneor more embodiments, the amount of isocyanate fed to the reactor may befrom about 1 to about 10, in other embodiments from about 2 to about 8,and in other embodiments from about 4 to about 6 percent by weight,based upon the total weight of the composition.

In one or more embodiments, the compositions of the present inventioninclude at least 0.25 in other embodiments at least 0.3, and in otherembodiments at least 0.4 percent by weight metal oxide based on thetotal weight of the composition. In these or other embodiments, thecompositions of the present invention include less than 0.6 in otherembodiments less than 0.8, and in other embodiments less than 1.0percent by weight metal oxide based on the total weight of thecomposition. In one or more embodiments, the amount of metal oxide fedto the reactor may be from about 0.25 to about 1.0, in other embodimentsfrom about 0.3 to about 0.8, and in other embodiments from about 0.4 toabout 0.6 percent by weight, based upon the total weight of thecomposition.

In one or more embodiments, the compositions of the present inventioninclude at least 50 ppm, in other embodiments at least 100 ppm, and inother embodiments at least 150 ppm polyurethane catalyst based on thetotal weight of the composition. In these or other embodiments, thecompositions of the present invention include less than 5,000 ppm, inother embodiments less than 4,000 ppm, and in other embodiments lessthan 3,000 ppm polyurethane catlyst based on the total weight of thecomposition. In one or more embodiments, the amount of polyurethanecatalyst fed to the reactor may be from about 50 to about 5,000 ppm, inother embodiments from about 100 to about 4,000 ppm, and in otherembodiments from about 150 to about 3,000 ppm, based upon the totalweight of the composition. In one or more embodiments, the polyurethanecatalyst can be delivered to the crosslinkable blend orpartially-crosslinked rubber as an oil solution or slurry. This blend orslurry may include from about 0.5 to about 10 weight percent, in otherembodiments from about 0.8 to about 5 weight percent, and in otherembodiments from 1 to 2 weight percent of the polyurethane catalyst,with the balance including an oil.

In one or more embodiments, the compositions of the present inventioninclude at least 15 in other embodiments at least 20, and in otherembodiments at least 25 percent by weight oil based on the total weightof the composition. In these or other embodiments, the compositions ofthe present invention include less than 55 in other embodiments lessthan 45, and in other embodiments less than 35 percent by weight oilbased on the total weight of the composition. In one or moreembodiments, the amount of oil fed to the reactor may be from about 15to about 55, in other embodiments from about 20 to about 45, and inother embodiments from about 25 to about 35 percent by weight, basedupon the total weight of the composition.

In one or more embodiments, the compositions of the present inventioninclude at least 0.1 in other embodiments at least 0.5, and in otherembodiments at least 1 percent by weight filler based on the totalweight of the composition. In these or other embodiments, thecompositions of the present invention include less than 5.0 in otherembodiments less than 3.0, and in other embodiments less than 2.5percent by weight filler based on the total weight of the composition.In one or more embodiments, the amount of filler fed to the reactor maybe from about 0.1 to about 5.0, in other embodiments from about 0.5 toabout 3.0, and in other embodiments from about 1 to about 2.5 percent byweight, based upon the total weight of the composition.

Product Characteristics

Advantageously, the adhesive composition demonstrates desirable tack andstrength without the need for further curing the composition.

In one or more embodiments, the composition of the present invention maybe characterized by including at least two phases at standard pressureand temperature. The first phase includes polyurethane domains and thesecond phase includes a butyl rubber matrix, wherein the polyurethanedomains are dispersed in the butyl rubber matrix.

In one or more embodiments, the composition may be characterized bybutyl rubber molecules that may be crosslinked through phenoliccrosslinks where methylene bridges or chemical bonds are formed betweenthe butyl rubber molecules. In these or other embodiments, the butylrubber molecules may be crosslinked or chemically bonded to thepolyurethane molecules. In one or more embodiments, these crosslinks mayexist as methylene bridges or crosslinks to the butyl rubber, and wherea hydroxyl group of the phenolic resin forms a polyurethane linkagebetween the phenolic resin and the polyurethane.

In one or more embodiments, the composition of the present invention mayinclude at least 35% by weight, in other embodiments at least 40% byweight, and in other embodiments at least 45% by weight butyl rubber,based upon the entire weight of the composition. In these or otherembodiments, the composition may include less than 65% by weight, inother embodiments less than 60% by weight, and in other embodiments lessthan 55% by weight butyl rubber, based upon the entire weight of thecomposition. In one or more embodiments, the amount of butyl rubberwithin the composition may be from about 35 to about 65, in otherembodiments from about 45 to about 60, and in other embodiments fromabout 40 to about 55 percent by weight, based upon the total weight ofthe composition.

In one or more embodiments, the composition may include at least 8% byweight, in other embodiments at least 10% by weight, and in otherembodiments at least 12% by weight polyurethane, based upon the entireweight of the composition. In these or other embodiments, thecomposition may include less than 20% by weight, in other embodimentsless than 18% by weight, and in other embodiments less than 16% byweight polyurethane, based on the entire weight of the composition. Inone or more embodiments, the amount of polyurethane within thecomposition may be from about 8 to about 20, in other embodiments fromabout 10 to about 18, and in other embodiments from about 12 to about 16percent by weight, based upon the total weight of the composition.

In one or more embodiments, the composition may include at least 25% byweight, in other embodiments at least 30% by weight, and in otherembodiments at least 35% by weight oil and other additives, based uponthe entire weight of the composition. In these or other embodiments, thecomposition may include less than 55% by weight, in other embodimentsless than 50% by weight, and in other embodiments less than 45% byweight oil and other additives, based upon the entire weight of thecomposition. In one or more embodiments, the amount of oil within thecomposition may be from about 25 to about 55, in other embodiments fromabout 30 to about 50, and in other embodiments from about 35 to about 45percent by weight, based upon the total weight of the composition.

In one or more embodiments, the polyurethane domains may becharacterized, at standard pressure and temperature, by a mean particlediameter of from about 0.1 μm to about 10 μm, in other embodiments fromabout 0.2 μm to about 5 μm, and in other embodiments from about 0.5 μmto about 2 μm.

In one or more embodiments, these discrete domains exist within thecomposition up to a temperature of about 37° C., in other embodimentsabout 55° C., in other embodiments about 80° C., in other embodimentsabout 100° C., and in other embodiments about 120° C. In one or moreembodiments, the polyurethane domains may be co-continuous with thebutyl rubber phase above these temperatures.

In one or more embodiments, the compositions may be characterized by apeel strength (ASTM D 413; aged 24 hours at room temperature and testedat room temperature) of at least 3.0 pounds per lineal inch (pli), inother embodiments at least 4.0 pli, and in other embodiments at least4.5 pli.

In one or more embodiments, the compositions may be characterized by apeel strength (ASTM D 413; aged 24 hours at 70° C. and tested at 70° C.)of at least 1.0 pli, in other embodiments at least 1.5 pli, and in otherembodiments at least 2.0 pli.

In one or more embodiments, the compositions may be characterized by atensile strength (ASTM D 412) of at least 40 psi, in other embodimentsat least 50 psi, and in other embodiments at least 55 psi.

In one or more embodiments, the compositions may be characterized by amaximum elongation (ASTM D 412) of at least 300 psi, in otherembodiments at least 400 psi, and in other embodiments at least 450 psi.

In one or more embodiments, the compositions pass a dead load sheartest. The dead load shear test includes measuring the separation of atest sample, and where the separation is less than ⅛″ (<3.17 mm), thesample is deemed to have passed the test. The overall test sample isprepared by adhering two EPDM strips together with a 1″×1″ adhesive seamsample, and the test includes placing the sample under the tension of a300 g weight for 24 hours at 158° F. The separation is measured as thedistance that the two EPDM strips separate.

INDUSTRIAL APPLICABILITY

The compositions of this invention may be used as a seam tape forroofing membranes. In particular embodiments, the roofing membranesinclude polymeric membranes, such as thermoset (e.g. EPDM) orthermoplastic (e.g. PVD or TPO) membranes, which are often used on flator low-sloped roofs.

In order to demonstrate the practice of the present invention, thefollowing examples have been prepared and tested. The examples shouldnot, however, be viewed as limiting the scope of the invention. Theclaims will serve to define the invention.

EXAMPLES

Several adhesive tape compositions were prepared within a twin-screwextruder having an L/D of 50/1. The ingredients employed and theoperating conditions of the extruder are set forth in Table I. As thoseskilled in the art will appreciate, the temperature profile within theextruder was adjusted to achieve the reported temperatures. Thecomposition was ultimately extruded onto a release paper and theadhesive tape composition was tested for a variety of physicalproperties, the test results of which are also set forth in Table I.

TABLE I Samples 1 2 3 4 5 6 7 8 9 10 Masterbatch 49.98 49.98 49.98 49.9849.98 49.98 49.98 49.98 0.00 0.00 Bromobutyl Rubber — — — — — — — —41.67 41.67 Polyenthlene Wax 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.002.75 2.75 Carbon Black 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 1.00 1.00Organomagnesium — — — — — — — — 0.00 1.18 Antioxidant 0.20 0.20 0.200.20 0.20 0.20 0.20 0.20 0.25 0.25 Unfunctionalized Phenolic Resin 3.163.16 3.16 3.16 3.16 3.16 3.16 3.16 8.34 8.34 High Viscosity PolybuteneOil 33.35 30.35 30.35 29.35 29.35 31.35 31.35 33.35 29.39 30.31Diisocyanate 1.50 2.00 2.00 2.50 2.50 1.50 1.50 1.50 5.00 5.00 AromaticOil 1.50 2.00 2.00 2.50 2.50 1.50 1.50 1.50 5.00 5.00 FunctionalizedPhenolic Resin I — — — — — — — — 2.00 0.00 Functionalized Phenolic ResinII — — — — — — — — 0.00 2.00 Amine Catalyst I — 3.00 3.00 3.00 3.00 3.003.00 — 3.00 0.00 Amine Catalyst II 1.00 — — — — — — 1.00 0.00 0.90Calcium Oxide 1.56 1.56 1.56 1.56 1.56 1.56 1.56 1.56 1.60 1.60Tackifier Resin 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 — — Total 100.00100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00Temperature (° F.), Actual Zone 1 103 109 111 111 110 110 110 100 103104 Zone 2 229 231 233 228 229 229 229 220 220 220 Zone 3 226 231 215211 232 229 217 200 211 214 Zone 4 216 230 199 200 248 224 190 208 208213 Zone 5 229 230 194 190 227 229 205 200 190 203 Zone 6 200 197 182181 197 201 171 178 179 182 Zone 7 199 192 180 180 201 200 175 180 180183 Zone 8 201 210 177 179 192 200 172 180 181 177 Zone 9 193 214 184179 198 199 185 185 181 179 Die 229 233 233 229 227 227 225 240 230 245AMP 26.5 — 27.4 26.7 27.1 26.6 26.5 25.3 27.2 27.2 Screw speed, rpm299.0 300.0 299.0 299.0 299.0 299.0 299.0 299.0 300.0 299.0 Torque, %44.0 — 46.0 43.0 42.0 44.0 40.0 31.0 43.0 43.0 Power, KW 2.2 — 2.4 2.22.3 2.2 — 1.8 2.2 2.2 Vac, psi 29.0 — 29.0 29.0 29.0 29.0 29.0 29.0 29.029.0 Die pressure, psi 697.0 — 707.0 676.0 808.0 688.0 — 372 849.0 719.0Lab 1 Test — — — — — — — — — — Dead Weight Shear 2.00 2.30 1.10 3.402.80 2.60 2.70 4.30 2.00 3.00 (158° F., mm) Failure type of DWS — — — —— — — — — — Peel Adhesion (1D 158° F./ 2.28 2.56 3.40 3.68 2.62 2.772.91 2.58 — — 158° F., pli)¹ Failure type of Peel 3A, 2B 5A 5A 5A 5A 5A1A, 4B 5A — — Peel Adhesion (1D 158° F./ — — — — — — — — 1.11 1.05 158°F., pli)¹ Failure type of Peel — — — — — — — — 4A, 1B 5A Tensile (psi)207 233 234 261 196 278 253 244 113 201 Thickness (in) 0.035 0.038 0.0380.035 0.034 0.036 0.035 0.034 0.036 0.036 100% Modulus (psi) 92 82 73 88110 105 76 74 49 95 200% Modulus (psi) 148 150 131 154 158 185 134 13368 143 300% Modulus (psi) 149 196 177 209 113 237 186 178 89 177Elongation @ Max load (%) 559 525 589 592 355 445 594 554 622 415¹Different Primers Employed

The solids ingredients, which included the rubber (or masterbatch), wax,carbon black, organomagnesium, antioxidant, phenolic resins(functionalized and unfunctionalized), calcium oxide, and tackifierresin, were added to the feed throat of the extruder. The pelletizedingredients were added by way of a pellet feeder and the powderedingredients were added by way of a powder feeder. In general, all of thesolids ingredients were added gravimetrically through a single hopperand the powder feeder and/or pellet feeder were used up stream of thegravimetric feeder to combine and disperse the ingredients prior togravimetric feeding. The rubber (or masterbatch) was added firstfollowed by the other solids ingredients. The liquid ingredients,including those ingredients dissolved or dispersed in oil, were addeddownstream at various locations. For example, the high viscositypolybutene oil was added at the third and seventh barrels by injectioninto the extruder. The diisocyanate, which was dissolved or dispersed inthe aromatic oil, was injected at the fifth barrel, and the aminecatalyst, which was likewise dispersed in an oil, was injected at thethird barrel.

The masterbatch was a blend of bromobutyl rubber and anon-functionalized phenolic resin obtained under the tradename SB-1068(SI Group); the masterbatch included 16.67 parts by weight phenolicresin per 100 parts by weight rubber. The bromobutyl rubber was obtainedunder the tradename Bromobutyl X-2 (Lanxess). The polyethylene wasobtained under the tradename Akrowax PE-LM (AkroChem). The carbon blackwas obtained under the tradename Black Pearls 880 (Cabot). Theorganomagnesium was obtained under the tradename TS33-59 (Resinall). Theantioxidant was obtained under the tradename Anox 20 (Chemtura). Theunfunctionalized phenolic resin was obtained under the tradename SP-1068(SI Group). The high viscosity polybutene oil was obtained under thetradename Indapol H-300 (INEOS). The diisocyanate was obtained under thetradename Rubinate 9433 (Huntsmen). The aromatic oil was obtained underthe tradename HB-40 (Solutia).The functionalized phenolic resin I wasobtained under the tradename SP1045 (SI Group). The functionalizedphenolic resin II was obtained under the tradename SP1055 (SI Group).The amine catalyst I was a triethylenediamine, which included 3.3% aminein Ruetasolv DI (Rutgers). The amine catalyst II was atriethylenediamine, which included 22% amine and neophenyl in IndapolH25 (INEOS). The tackifier resin was an aliphatic dicyclopentadienehydrocarbon resin, obtained under the tradename FT-11-46 (NevilleChemicals).

The dead weight shear was obtained on a test sample that included twoEPDM strips together with a 1″×1″ adhesive seam sample, and the testincluded placing the sample under the tension of a 300 g weight for 24hours at 158° F. The separation of the sample is reported inmillimeters. Peel adhesion was determined according to ASTM D413 afteraging at 70° C. for 24 hours with testing occurring at 70° C. Differentprimers were used as indicated in the table. Tensile, modulus, andelongation were determined according to ASTM D412.

Various modifications and alterations that do not depart from the scopeand spirit of this invention will become apparent to those skilled inthe art. This invention is not to be duly limited to the illustrativeembodiments set forth herein.

What is claimed is:
 1. A method for producing a polymeric composition,the method comprising: i. charging halogenated butyl rubber to areaction extruder; ii. charging a first phenolic resin to the reactionextruder, where the first phenolic resin includes functionality forreacting with double bonds located on the butyl rubber; iii. charging asecond phenolic resin that is substantially devoid of functionality forreacting with double bonds located on the butyl rubber; iv. charging ametal oxide to the reaction extruder; v. charging a catalyst to promotea reaction between the butyl rubber and the first phenolic resin to thereaction extruder; vi. mixing said halogenated butyl rubber, said firstphenolic resin, said metal oxide, and said catalyst to promote thereaction between the butyl rubber and the first phenolic resin tothereby partially crosslinking the rubber and functionalizing the rubberwith the first phenolic resin; vii. charging a isocyanate to thereaction extruder; and viii. mixing said partially crosslinked rubber,said phenolic resin, and said catalyst to thereby form a polyurethanedispersed within butyl rubber.
 2. The method of claim 1, where saidpolyurethane is phase-separated from said butyl rubber.
 3. The method ofclaim 1, where said polyurethane is cocontinuous with said butyl rubberat temperatures above 120° C.
 4. The method of claim 1, where theisocyanate is a diisocyanate, and where said polyurethane is thereaction product of said first phenolic resin and said diisocyanate. 5.A method for producing a polymer composition, the method comprising: i.providing a masterbatch composition that is prepared by combining ahalogenated butyl rubber with a phenolic resin; ii. introducing themasterbatch composition to a reactor; iii. introducing to the reactor anisocyanate and a catalyst for forming a polyurethane to form a blend;and iv. subjecting the blend to conditions sufficient to form apolyurethane.
 6. The method of claim 5, where the isocyanate is adiisocyanate.
 7. The method of claim 5, where the polyurethane is in theform of discrete domains within a matrix formed by the butyl rubber upto temperatures of at least 100° C.
 8. The method of claim 5, where thepolyurethane is in the form of discrete domains within a matrix formedby the butyl rubber up to temperatures of at least 120° C.
 9. The methodof claim 5, further comprising the step of introducing an oil to thereactor.
 10. The method of claim 5, further comprising the step ofintroducing a tackifier resin to the reactor.
 11. The method of claim 5,where the polyurethane is cocontinuous with the butyl rubber attemperatures above 120° C.
 12. A method for producing a polymericcomposition, the method comprising: i. providing a halogenated butylrubber including one or more halogen atoms and one or more double bondsderiving from isoprene; ii. partially cross-linking the butyl rubber bydisplacement of two or more of the halogen atoms by a metal oxide; iii.chemically binding a phenolic resin across one or more of the doublebonds to provide the butyl rubber with a hydroxyl functionality; iv.chemically binding an isocyanate to at least one hydroxyl functionalityof the butyl rubber to form a butyl rubber/urethane macromolecule; andv. forming a polyurethane in the presence of the butyl rubber/urethanemacromolecule.
 13. A phase-separated polymeric composition comprising:i. a first phase including polyurethane domains; and ii. a second phaseincluding a butyl rubber matrix, where the polyurethane includes merunits deriving from a phenolic resin and mer units deriving from adiisocyanate.
 14. The composition of claim 13, where the compositionfurther comprises an oil.
 15. The composition of claim 13, where thecomposition further comprises a tackifier resin.
 16. The composition ofclaim 13, where the butyl rubber is crosslinked.
 17. The composition ofclaim 13, where the polyurethane is bonded to the butyl rubber through aphenolic resin couple.
 18. The composition of claim 13, where thecomposition includes at least 8% by weight polyurethane based upon theentire weight of the composition.
 19. The composition of claim 18, wherethe composition includes at least 45% by weight butyl rubber, based uponthe entire weight of the composition.
 20. The composition of claim 13,where the composition demonstrates a peal strength (ASTM D413; aged 24hours at room temperature and tested at room temperature) of at least4.0 pounds per lineal inch.